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EP4108702B1 - Polylactide stereocomplex and preparation method therefor - Google Patents

Polylactide stereocomplex and preparation method therefor Download PDF

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Publication number
EP4108702B1
EP4108702B1 EP21864770.9A EP21864770A EP4108702B1 EP 4108702 B1 EP4108702 B1 EP 4108702B1 EP 21864770 A EP21864770 A EP 21864770A EP 4108702 B1 EP4108702 B1 EP 4108702B1
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EP
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Prior art keywords
poly
weight
lactate
hydroxypropionate
mol
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EP21864770.9A
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German (de)
French (fr)
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EP4108702A1 (en
EP4108702A4 (en
Inventor
Jung Yun Choi
Banseok CHOI
Chul Woong Kim
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LG Chem Ltd
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LG Chem Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
    • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2230/00—Compositions for preparing biodegradable polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
    • Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics

Definitions

  • the present invention relates to a polylactate stereocomplex including a poly(L-lactate-3-hydroxypropionate) block copolymer, and a preparation method thereof.
  • Polylactate (polylactide or polylactic acid) resin is a plant-derived resin obtained from plants such as corn, etc., and is attracting attention as an environment-friendly material having excellent tensile strength and elastic modulus while having biodegradable properties.
  • polylactate resin unlike petroleum-based resins such as polystyrene resin, polyvinyl chloride (PVC) resin, polyethylene, etc., which are currently used, polylactate resin has effects of preventing the depletion of petroleum resources, suppressing carbon dioxide emissions, etc., and thus it can reduce environmental pollution, which is a drawback of petroleum-based plastic products. Therefore, as the problem of environmental pollution caused by waste plastic, etc. has emerged as a social problem, it has been attempted to expand the scope of application to the fields of the products where general plastics (petroleum-based resins) were used, such as food packaging materials and containers, electronic product cases, etc.
  • the polylactate resin has low impact resistance and heat resistance, as compared with existing petroleum-based resins, and thus its application range is limited. Further, the polylactate resin has poor elongation characteristics and easily exhibits brittleness, which has a limitation as a general-purpose resin.
  • KR 2014 0147306 A discloses a polylactic acid stereocomplex resin composition
  • a polylactic acid stereocomplex resin composition comprising a crystalline poly L-lactic acid and a crystalline poly D-lactic acid having a weight average molecular weight of 40,000 to 200,000; and a method for preparing the composition, wherein the polylactic acid is a polyester-based resin manufactured by an esterification reaction using a lactic acid monomer.
  • polylactate stereocomplex having improved heat resistance and elongation characteristics while maintaining biodegradability, and a preparation method thereof.
  • a polylactate stereocomplex including:
  • a method of preparing a polylactate stereocomplex including the step of mixing a poly(L-lactate-3-hydroxypropionate) block copolymer including 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit and a poly(D-lactate) having a weight average molecular weight of 5,000 g/mol or more to less than 100,000 g/mol.
  • a polylactate stereocomplex of the present invention may have excellent physical properties such as heat resistance, elongation characteristics, etc. while maintaining biodegradability, thereby being suitably used as an eco-friendly general-purpose resin.
  • poly(L-lactate-3-hydroxypropionate) block copolymer refers to a block copolymer including a poly(L-lactate) repeating unit derived from an L-lactic acid monomer and/or an L-lactide monomer and a poly(3-hydroxypropionate) repeating unit derived from a 3-hydroxypropionate monomer, and may be expressed as "P(LLA-3-HP) block copolymer", or "P(LLA-b-3-HP)".
  • poly(L-lactate) is a homopolymer of an L-lactate monomer and/or an L-lactide monomer, and may be expressed as "PLLA”
  • poly(D-lactate) is a homopolymer of a D-lactic acid monomer and/or a D-lactide monomer, and may be expressed as "PDLA”.
  • Polylactate resin has biodegradability and biocompatibility, and thus is used as a representative biodegradable resin. However, it exhibits low thermal stability and elongation, which limits its use as a general-purpose alternative resin to polyolefin.
  • the present inventors have continued to study a material having excellent heat resistance and elongation characteristics while maintaining biodegradability, and as a result, they found that a poly(L-lactate-3-hydroxypropionate) block copolymer satisfying 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit is able to form a stereocomplex with poly(D-lactate), and this polylactate stereocomplex has remarkably improved heat resistance and elongation characteristics, as compared with the existing polylactate resins, thereby completing the present invention.
  • a polylactate stereocomplex including a poly(L-lactate-3-hydroxypropionate) block copolymer including 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit; and a poly(D-lactate) having a weight average molecular weight of 5,000 g/mol or more to less than 100,000 g/mol.
  • the poly(L-lactate-3-hydroxypropionate) block copolymer may exhibit excellent flexibility and tensile property due to the poly(3-hydroxypropionate) repeating unit, as compared with a poly(L-lactate) homopolymer, while maintaining crystallinity of the poly(L-lactate) repeating unit, thereby forming the stereocomplex with poly(D-lactate).
  • the poly(L-lactate) in the poly(L-lactate-3-hydroxypropionate) block copolymer may bind with the poly(D-lactate) like a zipper through an intermolecular bond such as a hydrogen bond, etc., and as a result, the polylactate stereocomplex of the present invention may exhibit excellent thermal stability and elongation characteristics.
  • the poly(L-lactate-3-hydroxypropionate) block copolymer of the present invention may preferably include 10 parts by weight or more to 50 parts by weight or less, for example, 10 parts by weight or more, or 20 parts by weight or more, and 50 parts by weight or less, or 45 parts by weight or less, or 40 parts by weight or less of the poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of the poly(L-lactate) repeating unit.
  • the content of the poly(3-hydroxypropionate) repeating unit is less than 10 parts by weight with respect to 100 parts by weight of the poly(L-lactate) repeating unit, it is difficult to secure the effect of improving physical properties of the polylactate stereocomplex, such as elongation, etc.
  • the content thereof is 50 parts by weight or more, the formation rate of the stereocomplex with poly(D-lactate) may be greatly reduced.
  • the poly(L-lactate-3-hydroxypropionate) block copolymer may have a weight average molecular weight of 10,000 g/mol or more, or 50,000 g/mol or more, or 70,000 g/mol or more, and 400,000 g/mol or less, or 300,000 g/mol or less, or 200,000 g/mol, or less, or 130,000 g/mol or less.
  • the weight average molecular weight of the poly(L-lactate-3-hydroxypropionate) block copolymer is less than 10,000 g/mol, it is difficult to obtain sufficient strength when the stereocomplex is formed. Further, when the weight average molecular weight of the poly(L-lactate-3-hydroxypropionate) block copolymer is more than 400,000 g/mol, there is a problem in that processing becomes difficult, and thus it is preferable to meet the above range.
  • the poly(L-lactate-3 -hydroxypropionate) block copolymer may have a melting temperature (Tm) of 145 °C or higher, 150 °C or higher, or 160 °C or higher.
  • Tm melting temperature
  • the melting temperature of the poly(L-lactate-3-hydroxypropionate) block copolymer may be, for example, 180 °C or lower.
  • the poly(L-lactate-3-hydroxypropionate) block copolymer meeting the content of the poly(3-hydroxypropionate) repeating unit may be prepared by the step of forming the poly(L-lactate) repeating unit and the poly(3-hydroxypropionate) repeating unit by ring-opening polymerization of the L-lactide monomer in the presence of a poly(3-hydroxypropionate) initiator.
  • the poly(3-hydroxypropionate) initiator may preferably have a weight average molecular weight of 1,500 g/mol to 50,000 g/mol, 2,000 g/mol to 40,000 g/mol, 4,000 g/mol to 45,000 g/mol, or 5,000 g/mol to 30,000 g/mol in order to allow the block copolymer to exhibit excellent physical properties without deterioration in the polymerization activity.
  • the poly(L-lactate-3-hydroxypropionate) block copolymer prepared from the poly(3-hydroxypropionate) initiator meeting the above molecular weight range may maintain crystallinity of the poly(L-lactate) repeating unit (block), thereby forming a stereocomplex with the poly(D-lactate).
  • a method of preparing the poly(L-lactate-3-hydroxypropionate) block copolymer suitable for formation of the polylactate stereocomplex of the present invention will be described in more detail in a description of a method of preparing the polylactate stereocomplex.
  • the poly(D-lactate) which forms the stereocomplex with the poly(L-lactate-3-hydroxypropionate) block copolymer is a homopolymer of a D-lactic acid monomer and/or a D-lactide monomer, and may have an optical purity of 90% or more, 95% or more, or 98% or more.
  • the poly(D-lactate) may preferably have a weight average molecular weight of 5,000 g/mol or more, or 7,000 g/mol or more, or 10,000 g/mol or more, or 15,000 g/mol or more, and 100,000 g/mol or less, 70,000 g/mol or less, or 50,000 g/mol or less.
  • weight average molecular weight of the poly(D-lactate) is less than 5,000 g/mol, there is a problem in that it is difficult to have sufficient crystallinity.
  • the weight average molecular weight of the poly(D-lactate) is more than 100,000 g/mol, it is difficult to achieve the effects of the present invention due to remarkable deterioration in the tensile and elongation characteristics of the prepared stereocomplex, and for this reason, it is preferable to meet the above range.
  • the weight average molecular weights of the poly(3-hydroxypropionate) initiator, the poly(L-lactate-3-hydroxypropionate) block copolymer, and the poly(D-lactate) may be measured by gel permeation chromatography (GPC) as in Examples described below.
  • the polylactate stereocomplex may include 70 parts by weight to 90 parts by weight of the poly(L-lactate-3-hydroxypropionate) block copolymer; and 10 parts by weight to 30 parts by weight of the poly(D-lactate).
  • the polylactate stereocomplex may include 80 parts by weight to 90 parts by weight of the poly(L-lactate-3-hydroxypropionate) block copolymer; and 10 parts by weight to 20 parts by weight of the poly(D-lactate).
  • the polylactate stereocomplex of the present invention exhibits remarkably improved heat resistance and elongation characteristics, as compared with the existing polylactate resins, because the poly(L-lactate-3-hydroxypropionate) block copolymer and the poly(D-lactate) form the complex, as described.
  • the polylactate stereocomplex may have a melting temperature (Tm) of 200 °C or higher, and 270 °C or lower, 260 °C or lower, 240 °C or lower, or 220 °C or lower.
  • Tm melting temperature
  • the polylactate stereocomplex When the melting temperature is 200 °C or higher, it may be determined that the polylactate stereocomplex has been formed. At this time, as a melting enthalpy is higher, it may be determined that the formation rate of the stereocomplex, i.e., the ratio of each polymer participating in the formation of the stereocomplex is higher. Accordingly, the polylactate stereocomplex according to one embodiment of the present invention may have a melting enthalpy of 11 J/g or more, or 20 J/g or more, and 50 J/g or less, or 45 J/g or less.
  • the melting temperature and the melting enthalpy may be measured by differential scanning calorimetry.
  • the polylactate stereocomplex may have elongation of 30 % or more, 45 % or more, or 55 % or more, as measured in accordance with IPC-TM-650 using a tensile strength tester after preparing a dogbone-shaped test specimen of ASTM D638 Type V, indicating that the polylactate stereocomplex exhibits remarkably excellent elongation, as compared with the existing stereocomplex of poly(L-lactate) and poly(D-lactate).
  • the upper limit of the elongation may be, but is not particularly limited to, for example, 150 % or less, or 110% or less.
  • the polylactate stereocomplex may be prepared by a preparation method including the step of mixing a poly(L-lactate-3-hydroxypropionate) block copolymer including 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit and a poly(D-lactate).
  • poly(L-lactate-3-hydroxypropionate) block copolymer and the poly(D-lactate) are the same as described above.
  • Methods of preparing the poly(L-lactate-3-hydroxypropionate) block copolymer and the poly(D-lactate) are not particularly limited, and known methods may be applied.
  • the poly(L-lactate-3-hydroxypropionate) block copolymer may be prepared by the step of forming the poly(L-lactate) repeating unit and poly(3-hydroxypropionate) repeating unit by ring-opening polymerization of the L-lactide monomer in the presence of a poly(3-hydroxypropionate) initiator.
  • the poly(3-hydroxypropionate) initiator includes a hydroxy group and/or an alkoxy group at the end.
  • the lactide monomer starts to be inserted from the end of the poly(3-hydroxypropionate) initiator, and as a result, the poly(L-lactate-3-hydroxypropionate) block copolymer may be prepared.
  • the poly(3-hydroxypropionate) serves as a polymerization initiator, and at the same time, is included as a repeating unit in the block copolymer, thereby making it possible to improve mechanical properties of the finally prepared block copolymer, such as flexibility, impact strength, etc.
  • the poly(3-hydroxypropionate) is included in the finally prepared block copolymer, it is possible to lower a glass transition temperature (Tg) of the block copolymer, thereby increasing the flexibility.
  • an input amount of the poly(3-hydroxypropionate) initiator may be selected within an appropriate range in consideration of the content of the repeating unit of poly(3-hydroxypropionate) included in the finally prepared block copolymer and a molar ratio of the hydroxy group and/or alkoxy group of the initiator which is required to initiate the minimum polymerization.
  • the poly(3-hydroxypropionate) initiator may be added in an amount of 10 parts by weight or more, or 20 parts by weight or more, and 50 parts by weight or less, or 40 parts by weight or less with respect to 100 parts by weight of the L-lactide monomer.
  • the poly(3-hydroxypropionate) initiator may have a weight average molecular weight of 1,500 g/mol to 50,000 g/mol, 2,000 g/mol to 40,000 g/mol, 4,000 g/mol to 45,000 g/mol, or 5,000 g/mol to 30,000 g/mol in order to exhibit excellent physical properties of the block copolymer without deteriorating polymerization activity.
  • the weight average molecular weight of the poly(3-hydroxypropionate) initiator is less than 1,500 g/mol, the content of poly(3-hydroxypropionate) may be reduced, and when the weight average molecular weight is more than 50,000 g/mol, the polymerization activity may be reduced.
  • 3-hydroxypropionate may be subjected to a condensation polymerization to prepare the poly(3-hydroxypropionate) initiator.
  • the reactant including the prepared poly(3-hydroxypropionate) initiator and lactide monomer is dried, and then the dried poly(3-hydroxypropionate) initiator and lactide monomer may be subjected to a ring-opening polymerization to prepare the above-mentioned block copolymer.
  • the catalyst used in the ring-opening polymerization all catalysts generally used in the preparation of polylactate resins by ring-opening polymerization of lactide monomers may be used.
  • the ring-opening polymerization may be performed in the presence of one or more catalysts selected from the group consisting of an organometallic complex catalyst and an organic catalyst.
  • the organometallic complex catalyst may be used without limitation in its composition, as long as it is generally used for preparing polylactate resins by ring-opening polymerization of lactide monomers.
  • the organometallic complex catalyst may be a catalyst represented by the following Chemical Formula 1: [Chemical Formula 1] MA 1 p A 2 2-p in Chemical Formula 1, M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti, or Zr, p is an integer of 0 to 2, and A 1 and A 2 are each independently an alkoxy or carboxyl group.
  • MA 1 p A 2 2-p may be tin (II) 2-ethylhexanoate (Sn(Oct) 2 ).
  • the organic catalyst may be used without limitation in its composition as long as it is generally used for preparing polylactate resins by ring-opening polymerization reaction of lactide monomers.
  • the organic catalyst may be one or more selected from the group consisting of the following 1,5,7-triazobicyclo-[4,4,0]dec-5-ene (TBD), the following 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), the following 7-methyl-1,5,7-triazabicyclo[4.4.0] dec-5-ene (MTBD), the following 4-dimethylaminopyridine (DMAP), the following 4-(1-pyrrolidinyl)pyridine (PPY), imidazole, triazolium, thiourea, tertiary amine, and creatinine.
  • TBD 1,5,7-triazobicyclo-[4,4,0]dec-5-ene
  • DBU 1,8-diazabicyclo[5.4.0]undec-7-
  • the imidazole may be one or more selected from the group consisting of the following compounds.
  • the triazolium may be the following compound.
  • the thiourea may be one or more selected from the group consisting of the following compounds.
  • the tertiary amine may be one or more selected from the group consisting of the following compounds.
  • the content of the catalyst may be 0.01 mol% to 10 mol%, 0.05 mol% to 8 mol%, 0.07 mol% to 5 mol%, or 0.09 mol% to 3 mol% with respect to 100 mol% of the lactide monomer.
  • the content of the catalyst is less than 0.01 mol% with respect to 100 mol% of the lactide monomer, polymerization activity may not be sufficient, and when the content of the catalyst is more than 10 mol%, the residual catalyst amount of the prepared poly(L-lactate-3-hydroxypropionate) block copolymer becomes larger, which may lead to decomposition or molecular weight reduction of the copolymer due to depolymerization such as transesterification reaction, etc.
  • the ring-opening polymerization may be performed at 150°C to 200°C for 5 minutes to 10 hours.
  • the ring-opening polymerization reaction may be performed by bulk polymerization using substantially no solvent.
  • "using substantially no solvent” may cover the case of using a small amount of a solvent for dissolving the catalyst, for example, the case of using up to less than 1 ml of the solvent per 1 kg of the used lactide monomer.
  • the ring-opening polymerization proceeds by bulk polymerization, it becomes possible to omit a process of removing the solvent after polymerization, and decomposition or loss of the resin in such a solvent removal process may also be suppressed.
  • the bulk polymerization the poly(L-lactate-3-hydroxypropionate) block copolymer may be obtained with high conversion and yield.
  • the poly(L-lactate-3-hydroxypropionate) block copolymer prepared as above maintains crystallinity of the poly(L-lactate) repeating unit, thereby forming the polylactate stereocomplex by polymerization with the poly(D-lactate).
  • the poly(D-lactate) may be a commercially available product, or may be prepared according to a known synthetic method.
  • the poly(D-lactate) may be prepared by condensation polymerization of a D-lactic acid monomer in the presence of a catalyst.
  • the poly(L-lactate-3-hydroxypropionate) block copolymer may be mixed with the poly(D-lactate) to prepare the stereocomplex.
  • a melt compounding method may be used, and in this case, a molecular weight of the prepared polylactate stereocomplex may be rather reduced.
  • the stereocomplex may be formed within a short time, and the formation rate of the complex may be high.
  • the melt compounding may be performed at a temperature of 140 °C to 200 °C, or 150 °C to 200 °C, or 170 °C to 200 °C. When the temperature during the melt compounding is lower than 140 °C, the formation rate of the stereocomplex may be lowered. When the temperature is excessively high by exceeding 200 °C, the polymer may be thermally deformed, and thus it is preferable to meet the above-mentioned range.
  • the melt compounding may be performed at atmospheric pressure, i.e., within a pressure range of 700 Torr to 800 Torr.
  • the poly(L-lactate-3-hydroxypropionate) block copolymer and the poly(D-lactate) may be stirred under the above temperature and pressure conditions for 20 minutes or more, or 30 minutes to 1 hour to prepare the polylactate stereocomplex.
  • a weight average molecular weight of the prepared poly(3-hydroxypropionate) oligomer (P3HP) was 10,000 g/mol.
  • the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 60 minutes to 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a P(LLA-b-3HP) copolymer having a weight average molecular weight of 124,000 g/mol.
  • a P(LLA-b-3HP) copolymer having a weight average molecular weight of 80,000 g/mol was prepared in the same manner as in Preparation Example 1-1, except that 100 parts by weight of L-lactide, 20 parts by weight of poly(3-hydroxypropionate) oligomer, and 0.01 mol% (with respect to 100% by weight of L-lactide) of tin(II) 2-ethylhexanoate were used in (2) of Preparation Example 1-1.
  • a weight average molecular weight of the prepared poly(3-hydroxypropionate) oligomer was 25,000 g/mol.
  • the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a P(LLA-b-3HP) copolymer having a weight average molecular weight of 115,100 g/mol.
  • a P(LLA-b-3HP) copolymer having a weight average molecular weight of 70,000 g/mol was prepared in the same manner as in Preparation Example 1-3, except that 100 parts by weight of L-lactide, 40 parts by weight of poly(3-hydroxypropionate) oligomer, and 0.01 mol% (with respect to 100% by weight of L-lactide) of tin(II) 2-ethylhexanoate were used in (2) of Preparation Example 1-3.
  • a P(LLA-b-3HP) copolymer having a weight average molecular weight of 30,000 g/mol was prepared in the same manner as in Preparation Example 1-3, except that 100 parts by weight of L-lactide, 70 parts by weight of poly(3-hydroxypropionate) oligomer, and 0.01 mol% (with respect to 100% by weight of L-lactide) of tin(II) 2-ethylhexanoate were used in (2) of Preparation Example 1-3.
  • the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a PLLA polymer having a weight average molecular weight of 118,000 g/mol.
  • the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a PDLA polymer having a weight average molecular weight of 50,000 g/mol.
  • the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a PDLA polymer having a weight average molecular weight of 120,000 g/mol.
  • Each polylactate stereocomplex was prepared in the same manner as in Example 1, except that substances described in Table 2 below were used as P(LLA-b-3HP) (or PLLA) and PDLA, and the content of PDLA was controlled as described in Table 2 below.
  • a weight average molecular weight (Mw) and a number average molecular weight (Mn) of each polymer were determined by gel permeation chromatography (GPC) (Waters: Waters707).
  • a polydispersity index (PDI) was calculated by dividing the measured weight average molecular weight by the number average molecular weight.
  • the polymer to be measured was dissolved in chloroform to a concentration of 4000 ppm, and 100 ⁇ l thereof was injected into GPC.
  • Chloroform was used as a mobile phase of GPC, a flow rate was 1.0 mL/min, and analysis was performed at 35°C.
  • As a column four Waters HR-05,1,2,4E were connected in series. RI and PAD detectors were used as detectors, and the measurement was performed at 35°C.
  • a melting enthalpy and a melting temperature were measured using a differential scanning calorimeter (DSC, manufacturer: Mettler Toledo) by the following method.
  • the polymer (or stereocomplex) was heated to 230 °C, and then maintained for 5 minutes, and the temperature was decreased to -40 °C to remove thermal history, and then heated to 230 °C and the melting temperature (Tm) and the melting enthalpy ( ⁇ H) were measured from a peak of the secondary heating. At this time, the heating and cooling rates were controlled to 10 °C/min, respectively.
  • Elongation was measured for the stereocomplexes of Examples 1 to 6 and Comparative Example 1, and the P(LLA-b-3HP) copolymer of Preparation Example 1-3 by the following method.
  • Each dogbone-shaped test specimen corresponding to ASTM D638 Type V was prepared at 170 °C using a hot-press (Limotem QM900S) device.
  • Comparative Example 2 in which P(LLA-b-3HP) including more than 50 parts by weight of the poly(3-hydroxypropionate) repeating unit was used, exhibited the melting temperature of lower than 200 °C, indicating that the complex was not formed. Further, Comparative Example 3, in which PDLA having a weight average molecular weight of more than 100,000 g/mol was used, showed formation of the stereocomplex, but its tensile elongation characteristic was remarkably reduced, as compared with those of Examples 1 to 6.

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Description

    [Technical Field]
  • The present invention relates to a polylactate stereocomplex including a poly(L-lactate-3-hydroxypropionate) block copolymer, and a preparation method thereof.
    • [Background Art]
  • Polylactate (polylactide or polylactic acid) resin is a plant-derived resin obtained from plants such as corn, etc., and is attracting attention as an environment-friendly material having excellent tensile strength and elastic modulus while having biodegradable properties. Specifically, unlike petroleum-based resins such as polystyrene resin, polyvinyl chloride (PVC) resin, polyethylene, etc., which are currently used, polylactate resin has effects of preventing the depletion of petroleum resources, suppressing carbon dioxide emissions, etc., and thus it can reduce environmental pollution, which is a drawback of petroleum-based plastic products. Therefore, as the problem of environmental pollution caused by waste plastic, etc. has emerged as a social problem, it has been attempted to expand the scope of application to the fields of the products where general plastics (petroleum-based resins) were used, such as food packaging materials and containers, electronic product cases, etc.
  • However, the polylactate resin has low impact resistance and heat resistance, as compared with existing petroleum-based resins, and thus its application range is limited. Further, the polylactate resin has poor elongation characteristics and easily exhibits brittleness, which has a limitation as a general-purpose resin.
  • Accordingly, to enhance the elongation characteristics of the polylactate resin, a method of compounding an additive or forming a copolymer with a functional monomer, or to enhance heat resistance, a method of adding a nucleating agent or an inorganic additive, etc. has been proposed. However, the additives used in these methods have a problem in that most of them are not biodegradable.
  • Accordingly, it is required to develop a material exhibiting improved heat resistance and elongation characteristics while maintaining biodegradability.
  • KR 2014 0147306 A discloses a polylactic acid stereocomplex resin composition comprising a crystalline poly L-lactic acid and a crystalline poly D-lactic acid having a weight average molecular weight of 40,000 to 200,000; and a method for preparing the composition, wherein the polylactic acid is a polyester-based resin manufactured by an esterification reaction using a lactic acid monomer.
  • Journal of Polymer Science Part A: Polymer Chemistry, Vol. 50, No. 7, pages 1445-1455, discloses poly(3-hydroxyalkanoate)-b-poly(D,L)-lactide diblock copolymer.
    • [Disclosure] [Technical Problem]
  • There are provided a polylactate stereocomplex having improved heat resistance and elongation characteristics while maintaining biodegradability, and a preparation method thereof.
    • [Technical Solution]
  • According to one aspect of the present invention, provided is a polylactate stereocomplex including:
    • a poly(L-lactate-3-hydroxypropionate) block copolymer including 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit; and
    • a poly(D-lactate) having a weight average molecular weight of 5,000 g/mol or more to less than 100,000 g/mol.
  • According to another aspect of the present invention, provided is a method of preparing a polylactate stereocomplex, the method including the step of mixing a poly(L-lactate-3-hydroxypropionate) block copolymer including 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit and a poly(D-lactate) having a weight average molecular weight of 5,000 g/mol or more to less than 100,000 g/mol.
    • [Effect of the Invention]
  • A polylactate stereocomplex of the present invention may have excellent physical properties such as heat resistance, elongation characteristics, etc. while maintaining biodegradability, thereby being suitably used as an eco-friendly general-purpose resin.
    • [Detailed Description of the Embodiments]
  • The terms used in this description are just for explaining exemplary embodiments and it is not intended to restrict the present invention. The singular expression may include the plural expression unless it is differently expressed contextually. It must be understood that the term "include", "equip", or "have" in the present description is only used for designating the existence of characteristics taken effect, steps, components, or combinations thereof, and do not exclude the existence or the possibility of addition of one or more different characteristics, steps, components or combinations thereof beforehand.
  • As used herein, the "poly(L-lactate-3-hydroxypropionate) block copolymer" refers to a block copolymer including a poly(L-lactate) repeating unit derived from an L-lactic acid monomer and/or an L-lactide monomer and a poly(3-hydroxypropionate) repeating unit derived from a 3-hydroxypropionate monomer, and may be expressed as "P(LLA-3-HP) block copolymer", or "P(LLA-b-3-HP)".
  • Further, as used herein, the "poly(L-lactate)" is a homopolymer of an L-lactate monomer and/or an L-lactide monomer, and may be expressed as "PLLA", and the "poly(D-lactate)" is a homopolymer of a D-lactic acid monomer and/or a D-lactide monomer, and may be expressed as "PDLA".
  • Hereinafter, the present invention will be described in detail.
    • Polylactate stereocomplex
  • Polylactate resin has biodegradability and biocompatibility, and thus is used as a representative biodegradable resin. However, it exhibits low thermal stability and elongation, which limits its use as a general-purpose alternative resin to polyolefin.
  • Accordingly, the present inventors have continued to study a material having excellent heat resistance and elongation characteristics while maintaining biodegradability, and as a result, they found that a poly(L-lactate-3-hydroxypropionate) block copolymer satisfying 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit is able to form a stereocomplex with poly(D-lactate), and this polylactate stereocomplex has remarkably improved heat resistance and elongation characteristics, as compared with the existing polylactate resins, thereby completing the present invention.
  • According to one aspect of the present invention, provided is a polylactate stereocomplex including a poly(L-lactate-3-hydroxypropionate) block copolymer including 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit; and a poly(D-lactate) having a weight average molecular weight of 5,000 g/mol or more to less than 100,000 g/mol.
  • The poly(L-lactate-3-hydroxypropionate) block copolymer may exhibit excellent flexibility and tensile property due to the poly(3-hydroxypropionate) repeating unit, as compared with a poly(L-lactate) homopolymer, while maintaining crystallinity of the poly(L-lactate) repeating unit, thereby forming the stereocomplex with poly(D-lactate).
  • In other words, the poly(L-lactate) in the poly(L-lactate-3-hydroxypropionate) block copolymer may bind with the poly(D-lactate) like a zipper through an intermolecular bond such as a hydrogen bond, etc., and as a result, the polylactate stereocomplex of the present invention may exhibit excellent thermal stability and elongation characteristics.
  • To meet the above characteristics, the poly(L-lactate-3-hydroxypropionate) block copolymer of the present invention may preferably include 10 parts by weight or more to 50 parts by weight or less, for example, 10 parts by weight or more, or 20 parts by weight or more, and 50 parts by weight or less, or 45 parts by weight or less, or 40 parts by weight or less of the poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of the poly(L-lactate) repeating unit.
  • When the content of the poly(3-hydroxypropionate) repeating unit is less than 10 parts by weight with respect to 100 parts by weight of the poly(L-lactate) repeating unit, it is difficult to secure the effect of improving physical properties of the polylactate stereocomplex, such as elongation, etc. When the content thereof is 50 parts by weight or more, the formation rate of the stereocomplex with poly(D-lactate) may be greatly reduced.
  • Meanwhile, the poly(L-lactate-3-hydroxypropionate) block copolymer may have a weight average molecular weight of 10,000 g/mol or more, or 50,000 g/mol or more, or 70,000 g/mol or more, and 400,000 g/mol or less, or 300,000 g/mol or less, or 200,000 g/mol, or less, or 130,000 g/mol or less.
  • When the weight average molecular weight of the poly(L-lactate-3-hydroxypropionate) block copolymer is less than 10,000 g/mol, it is difficult to obtain sufficient strength when the stereocomplex is formed. Further, when the weight average molecular weight of the poly(L-lactate-3-hydroxypropionate) block copolymer is more than 400,000 g/mol, there is a problem in that processing becomes difficult, and thus it is preferable to meet the above range.
  • Further, the poly(L-lactate-3 -hydroxypropionate) block copolymer may have a melting temperature (Tm) of 145 °C or higher, 150 °C or higher, or 160 °C or higher. The melting temperature of the poly(L-lactate-3-hydroxypropionate) block copolymer may be, for example, 180 °C or lower.
  • The poly(L-lactate-3-hydroxypropionate) block copolymer meeting the content of the poly(3-hydroxypropionate) repeating unit may be prepared by the step of forming the poly(L-lactate) repeating unit and the poly(3-hydroxypropionate) repeating unit by ring-opening polymerization of the L-lactide monomer in the presence of a poly(3-hydroxypropionate) initiator.
  • At this time, the poly(3-hydroxypropionate) initiator may preferably have a weight average molecular weight of 1,500 g/mol to 50,000 g/mol, 2,000 g/mol to 40,000 g/mol, 4,000 g/mol to 45,000 g/mol, or 5,000 g/mol to 30,000 g/mol in order to allow the block copolymer to exhibit excellent physical properties without deterioration in the polymerization activity.
  • The poly(L-lactate-3-hydroxypropionate) block copolymer prepared from the poly(3-hydroxypropionate) initiator meeting the above molecular weight range may maintain crystallinity of the poly(L-lactate) repeating unit (block), thereby forming a stereocomplex with the poly(D-lactate).
  • A method of preparing the poly(L-lactate-3-hydroxypropionate) block copolymer suitable for formation of the polylactate stereocomplex of the present invention will be described in more detail in a description of a method of preparing the polylactate stereocomplex.
  • The poly(D-lactate) which forms the stereocomplex with the poly(L-lactate-3-hydroxypropionate) block copolymer is a homopolymer of a D-lactic acid monomer and/or a D-lactide monomer, and may have an optical purity of 90% or more, 95% or more, or 98% or more.
  • The poly(D-lactate) may preferably have a weight average molecular weight of 5,000 g/mol or more, or 7,000 g/mol or more, or 10,000 g/mol or more, or 15,000 g/mol or more, and 100,000 g/mol or less, 70,000 g/mol or less, or 50,000 g/mol or less. When the weight average molecular weight of the poly(D-lactate) is less than 5,000 g/mol, there is a problem in that it is difficult to have sufficient crystallinity. When the weight average molecular weight of the poly(D-lactate) is more than 100,000 g/mol, it is difficult to achieve the effects of the present invention due to remarkable deterioration in the tensile and elongation characteristics of the prepared stereocomplex, and for this reason, it is preferable to meet the above range.
  • The weight average molecular weights of the poly(3-hydroxypropionate) initiator, the poly(L-lactate-3-hydroxypropionate) block copolymer, and the poly(D-lactate) may be measured by gel permeation chromatography (GPC) as in Examples described below.
  • The polylactate stereocomplex may include 70 parts by weight to 90 parts by weight of the poly(L-lactate-3-hydroxypropionate) block copolymer; and 10 parts by weight to 30 parts by weight of the poly(D-lactate). As described, when the content of the poly(L-lactate-3-hydroxypropionate) block copolymer is high, mechanical properties of the prepared polylactate stereocomplex may be further improved. More preferably, the polylactate stereocomplex may include 80 parts by weight to 90 parts by weight of the poly(L-lactate-3-hydroxypropionate) block copolymer; and 10 parts by weight to 20 parts by weight of the poly(D-lactate).
  • The polylactate stereocomplex of the present invention exhibits remarkably improved heat resistance and elongation characteristics, as compared with the existing polylactate resins, because the poly(L-lactate-3-hydroxypropionate) block copolymer and the poly(D-lactate) form the complex, as described.
  • Specifically, the polylactate stereocomplex may have a melting temperature (Tm) of 200 °C or higher, and 270 °C or lower, 260 °C or lower, 240 °C or lower, or 220 °C or lower.
  • When the melting temperature is 200 °C or higher, it may be determined that the polylactate stereocomplex has been formed. At this time, as a melting enthalpy is higher, it may be determined that the formation rate of the stereocomplex, i.e., the ratio of each polymer participating in the formation of the stereocomplex is higher. Accordingly, the polylactate stereocomplex according to one embodiment of the present invention may have a melting enthalpy of 11 J/g or more, or 20 J/g or more, and 50 J/g or less, or 45 J/g or less.
  • The melting temperature and the melting enthalpy may be measured by differential scanning calorimetry.
  • Meanwhile, the polylactate stereocomplex may have elongation of 30 % or more, 45 % or more, or 55 % or more, as measured in accordance with IPC-TM-650 using a tensile strength tester after preparing a dogbone-shaped test specimen of ASTM D638 Type V, indicating that the polylactate stereocomplex exhibits remarkably excellent elongation, as compared with the existing stereocomplex of poly(L-lactate) and poly(D-lactate). The upper limit of the elongation may be, but is not particularly limited to, for example, 150 % or less, or 110% or less.
  • Methods of measuring the melting temperature, the melting enthalpy, and the elongation characteristics of the polylactate stereocomplex will be described in more detail in Examples below.
    • Method of preparing polylactate stereocomplex
  • Meanwhile, according to another aspect of the present invention, provided is a method of preparing the above-described polylactate stereocomplex.
  • Specifically, the polylactate stereocomplex may be prepared by a preparation method including the step of mixing a poly(L-lactate-3-hydroxypropionate) block copolymer including 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit and a poly(D-lactate).
  • Features of the poly(L-lactate-3-hydroxypropionate) block copolymer and the poly(D-lactate) are the same as described above.
  • Methods of preparing the poly(L-lactate-3-hydroxypropionate) block copolymer and the poly(D-lactate) are not particularly limited, and known methods may be applied.
  • For example, the poly(L-lactate-3-hydroxypropionate) block copolymer may be prepared by the step of forming the poly(L-lactate) repeating unit and poly(3-hydroxypropionate) repeating unit by ring-opening polymerization of the L-lactide monomer in the presence of a poly(3-hydroxypropionate) initiator.
  • The poly(3-hydroxypropionate) initiator includes a hydroxy group and/or an alkoxy group at the end. Thus, when the poly(3-hydroxypropionate) initiator is added to the ring-opening polymerization reaction of the lactide monomer, the lactide monomer starts to be inserted from the end of the poly(3-hydroxypropionate) initiator, and as a result, the poly(L-lactate-3-hydroxypropionate) block copolymer may be prepared.
  • Therefore, when the ring-opening polymerization reaction of the lactide monomer is performed in the presence of the poly(3-hydroxypropionate) initiator, the poly(3-hydroxypropionate) serves as a polymerization initiator, and at the same time, is included as a repeating unit in the block copolymer, thereby making it possible to improve mechanical properties of the finally prepared block copolymer, such as flexibility, impact strength, etc. Specifically, since the poly(3-hydroxypropionate) is included in the finally prepared block copolymer, it is possible to lower a glass transition temperature (Tg) of the block copolymer, thereby increasing the flexibility.
  • In this regard, an input amount of the poly(3-hydroxypropionate) initiator may be selected within an appropriate range in consideration of the content of the repeating unit of poly(3-hydroxypropionate) included in the finally prepared block copolymer and a molar ratio of the hydroxy group and/or alkoxy group of the initiator which is required to initiate the minimum polymerization.
  • Specifically, in consideration of the minimum content for maintaining crystallinity of the poly(L-lactate) repeating unit of the finally prepared block copolymer while optimizing the flexibility and mechanical properties thereof, and for acting as an initiator of the ring-opening polymerization reaction, the poly(3-hydroxypropionate) initiator may be added in an amount of 10 parts by weight or more, or 20 parts by weight or more, and 50 parts by weight or less, or 40 parts by weight or less with respect to 100 parts by weight of the L-lactide monomer.
  • The poly(3-hydroxypropionate) initiator may have a weight average molecular weight of 1,500 g/mol to 50,000 g/mol, 2,000 g/mol to 40,000 g/mol, 4,000 g/mol to 45,000 g/mol, or 5,000 g/mol to 30,000 g/mol in order to exhibit excellent physical properties of the block copolymer without deteriorating polymerization activity. When the weight average molecular weight of the poly(3-hydroxypropionate) initiator is less than 1,500 g/mol, the content of poly(3-hydroxypropionate) may be reduced, and when the weight average molecular weight is more than 50,000 g/mol, the polymerization activity may be reduced.
  • On the other hand, before the ring-opening polymerization step, 3-hydroxypropionate may be subjected to a condensation polymerization to prepare the poly(3-hydroxypropionate) initiator. The reactant including the prepared poly(3-hydroxypropionate) initiator and lactide monomer is dried, and then the dried poly(3-hydroxypropionate) initiator and lactide monomer may be subjected to a ring-opening polymerization to prepare the above-mentioned block copolymer.
  • As the catalyst used in the ring-opening polymerization, all catalysts generally used in the preparation of polylactate resins by ring-opening polymerization of lactide monomers may be used. For example, the ring-opening polymerization may be performed in the presence of one or more catalysts selected from the group consisting of an organometallic complex catalyst and an organic catalyst.
  • The organometallic complex catalyst may be used without limitation in its composition, as long as it is generally used for preparing polylactate resins by ring-opening polymerization of lactide monomers. For example, the organometallic complex catalyst may be a catalyst represented by the following Chemical Formula 1:

            [Chemical Formula 1]     MA1 pA2 2-p

    in Chemical Formula 1, M is Al, Mg, Zn, Ca, Sn, Fe, Y, Sm, Lu, Ti, or Zr, p is an integer of 0 to 2, and A1 and A2 are each independently an alkoxy or carboxyl group.
  • More specifically, MA1 pA2 2-p may be tin (II) 2-ethylhexanoate (Sn(Oct)2).
  • On the other hand, the organic catalyst may be used without limitation in its composition as long as it is generally used for preparing polylactate resins by ring-opening polymerization reaction of lactide monomers. For example, the organic catalyst may be one or more selected from the group consisting of the following 1,5,7-triazobicyclo-[4,4,0]dec-5-ene (TBD), the following 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU), the following 7-methyl-1,5,7-triazabicyclo[4.4.0] dec-5-ene (MTBD), the following 4-dimethylaminopyridine (DMAP), the following 4-(1-pyrrolidinyl)pyridine (PPY), imidazole, triazolium, thiourea, tertiary amine, and creatinine.
    Figure imgb0001
  • The imidazole may be one or more selected from the group consisting of the following compounds.
    Figure imgb0002
    Figure imgb0003
  • The triazolium may be the following compound.
    Figure imgb0004
  • The thiourea may be one or more selected from the group consisting of the following compounds.
    Figure imgb0005
  • The tertiary amine may be one or more selected from the group consisting of the following compounds.
    Figure imgb0006
  • When the lactide ring-opening polymerization reaction proceeds in the presence of the above-mentioned catalyst, depolymerization or decomposition of the finally prepared block copolymer may be suppressed, and a poly(L-lactate-3-hydroxypropionate) block copolymer having a higher molecular weight and excellent mechanical properties may be obtained with a higher conversion rate.
  • In the method of preparing the block copolymer according to an aspect, the content of the catalyst may be 0.01 mol% to 10 mol%, 0.05 mol% to 8 mol%, 0.07 mol% to 5 mol%, or 0.09 mol% to 3 mol% with respect to 100 mol% of the lactide monomer. When the content of the catalyst is less than 0.01 mol% with respect to 100 mol% of the lactide monomer, polymerization activity may not be sufficient, and when the content of the catalyst is more than 10 mol%, the residual catalyst amount of the prepared poly(L-lactate-3-hydroxypropionate) block copolymer becomes larger, which may lead to decomposition or molecular weight reduction of the copolymer due to depolymerization such as transesterification reaction, etc.
  • The ring-opening polymerization may be performed at 150°C to 200°C for 5 minutes to 10 hours.
  • Further, the ring-opening polymerization reaction may be performed by bulk polymerization using substantially no solvent. At this time, "using substantially no solvent" may cover the case of using a small amount of a solvent for dissolving the catalyst, for example, the case of using up to less than 1 ml of the solvent per 1 kg of the used lactide monomer. As the ring-opening polymerization proceeds by bulk polymerization, it becomes possible to omit a process of removing the solvent after polymerization, and decomposition or loss of the resin in such a solvent removal process may also be suppressed. In addition, by the bulk polymerization, the poly(L-lactate-3-hydroxypropionate) block copolymer may be obtained with high conversion and yield.
  • The poly(L-lactate-3-hydroxypropionate) block copolymer prepared as above maintains crystallinity of the poly(L-lactate) repeating unit, thereby forming the polylactate stereocomplex by polymerization with the poly(D-lactate).
  • Meanwhile, the poly(D-lactate) may be a commercially available product, or may be prepared according to a known synthetic method. In one embodiment, the poly(D-lactate) may be prepared by condensation polymerization of a D-lactic acid monomer in the presence of a catalyst.
  • Next, the poly(L-lactate-3-hydroxypropionate) block copolymer may be mixed with the poly(D-lactate) to prepare the stereocomplex. At this time, a melt compounding method may be used, and in this case, a molecular weight of the prepared polylactate stereocomplex may be rather reduced. However, the stereocomplex may be formed within a short time, and the formation rate of the complex may be high.
  • The melt compounding may be performed at a temperature of 140 °C to 200 °C, or 150 °C to 200 °C, or 170 °C to 200 °C. When the temperature during the melt compounding is lower than 140 °C, the formation rate of the stereocomplex may be lowered. When the temperature is excessively high by exceeding 200 °C, the polymer may be thermally deformed, and thus it is preferable to meet the above-mentioned range. The melt compounding may be performed at atmospheric pressure, i.e., within a pressure range of 700 Torr to 800 Torr. The poly(L-lactate-3-hydroxypropionate) block copolymer and the poly(D-lactate) may be stirred under the above temperature and pressure conditions for 20 minutes or more, or 30 minutes to 1 hour to prepare the polylactate stereocomplex.
  • Hereinafter, preferred exemplary embodiments will be provided for better understanding of the present invention. However, the following exemplary embodiments are only for illustrating the present invention.
    • [Preparation Example] Preparation Example 1-1: Preparation of poly(L-lactate-3-hydroxypropionate) block copolymer (1) Preparation of poly(3-hydroxypropionate) oligomer
  • 30 g (416 mmol) of 3-hydroxypropionate was dried, and then subjected to condensation polymerization in the presence of 0.012 g of a p-toluene sulfonic acid (p-TSA) catalyst under conditions of a temperature of 110 °C and a reduced pressure of 0.1 Torr for 12 hours to prepare a poly(3-hydroxypropionate) oligomer.
  • A weight average molecular weight of the prepared poly(3-hydroxypropionate) oligomer (P3HP) was 10,000 g/mol.
    • (2) Preparation of poly(L-lactate-3-hydroxypropionate) block copolymer
  • In a 100 mL round flask, 100 parts by weight of L-lactide, 10 parts by weight of the poly(3-hydroxypropionate) oligomer prepared in (1), and 0.01 mol% (with respect to 100% by weight of L-lactide) of tin(II) 2-ethylhexanoate were put and vacuum-dried at room temperature for 4 hours by sufficiently applying a vacuum.
  • Thereafter, the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 60 minutes to 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a P(LLA-b-3HP) copolymer having a weight average molecular weight of 124,000 g/mol.
    • Preparation Example 1-2: Preparation of poly(L-lactate-3-hydroxypropionate) block copolymer
  • A P(LLA-b-3HP) copolymer having a weight average molecular weight of 80,000 g/mol was prepared in the same manner as in Preparation Example 1-1, except that 100 parts by weight of L-lactide, 20 parts by weight of poly(3-hydroxypropionate) oligomer, and 0.01 mol% (with respect to 100% by weight of L-lactide) of tin(II) 2-ethylhexanoate were used in (2) of Preparation Example 1-1.
    • Preparation Example 1-3: Preparation of poly(L-lactate-3-hydroxypropionate) block copolymer (1) Preparation of poly(3-hydroxypropionate) oligomer
  • 30 g (416 mmol) of 3-hydroxypropionate was dried, and then subjected to condensation polymerization in the presence of 0.012 g of a p-toluene sulfonic acid (p-TSA) catalyst under conditions of a temperature of 110 °C and a reduced pressure of 0.1 Torr for 24 hours to prepare a poly(3-hydroxypropionate) oligomer.
  • A weight average molecular weight of the prepared poly(3-hydroxypropionate) oligomer was 25,000 g/mol.
    • (2) Preparation of poly(L-lactate-3-hydroxypropionate) block copolymer
  • In a 100 mL round flask, 100 parts by weight of L-lactide, 20 parts by weight of the poly(3-hydroxypropionate) oligomer prepared in (1), and 0.01 mol% (with respect to 100% by weight of L-lactide) of tin(II) 2-ethylhexanoate were put and vacuum-dried at room temperature for 4 hours by sufficiently applying a vacuum.
  • Thereafter, the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a P(LLA-b-3HP) copolymer having a weight average molecular weight of 115,100 g/mol.
    • Preparation Example 1-4: Preparation of poly(L-lactate-3-hydroxypropionate) block copolymer
  • A P(LLA-b-3HP) copolymer having a weight average molecular weight of 70,000 g/mol was prepared in the same manner as in Preparation Example 1-3, except that 100 parts by weight of L-lactide, 40 parts by weight of poly(3-hydroxypropionate) oligomer, and 0.01 mol% (with respect to 100% by weight of L-lactide) of tin(II) 2-ethylhexanoate were used in (2) of Preparation Example 1-3.
    • Preparation Example 1-5: Preparation of poly(L-lactate-3-hydroxypropionate) block copolymer
  • A P(LLA-b-3HP) copolymer having a weight average molecular weight of 30,000 g/mol was prepared in the same manner as in Preparation Example 1-3, except that 100 parts by weight of L-lactide, 70 parts by weight of poly(3-hydroxypropionate) oligomer, and 0.01 mol% (with respect to 100% by weight of L-lactide) of tin(II) 2-ethylhexanoate were used in (2) of Preparation Example 1-3.
    • Preparation Example 1-6: Preparation of poly(L-lactate)
  • In a 500 mL round flask, 25 g of L-lactide, and 11.2 µl (0.01 mol% with respect to 100% by weight of L-lactide) of tin(II) 2-ethylhexanoate were put and vacuum-dried at room temperature (25 °C) for 4 hours by sufficiently applying a vacuum.
  • Thereafter, the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a PLLA polymer having a weight average molecular weight of 118,000 g/mol.
    • Preparation Example 2-1: Preparation of poly(D-lactate)
  • In a 100 mL round flask, 20 g of D-lactic acid and 6 g of p-toluenesufonic acid catalyst were put and allowed to react under conditions of 50 mbar and 110 °C for 3 hours and under conditions of 20 mbar and 140 °C for 15 hours to obtain a PDLA polymer having a weight average molecular weight of 14,690 g/mol.
    • Preparation Example 2-2: Preparation of poly(D-lactate)
  • In a 100 mL round flask, 10 g (70 mmol) of D-lactide, 0.036 g (0.2 mmol) of 1-octanol, and 0.01 mol% (with respect to 100% by weight of D-lactide) of tin(II) 2-ethylhexanoate were put and vacuum-dried at room temperature for 4 hours by sufficiently applying a vacuum.
  • Thereafter, the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a PDLA polymer having a weight average molecular weight of 50,000 g/mol.
    • Preparation Example 2-3: Preparation of poly(D-lactate)
  • In a 100 mL round flask, 10 g (70 mmol) of D-lactide, 0.016 g (0.1 mmol) of 1-octanol, and 0.01 mol% (with respect to 100% by weight of D-lactide) of tin(II) 2-ethylhexanoate were put and vacuum-dried at room temperature for 4 hours by sufficiently applying a vacuum.
  • Thereafter, the flask was placed in an oil bath pre-heated at 130°C, the temperature of which was raised to 180°C, and then a ring-opening polymerization reaction was carried out for 90 minutes. After the reaction was completed, the reaction product was dissolved in chloroform and then extracted with methanol to recover a PDLA polymer having a weight average molecular weight of 120,000 g/mol.
    • Example 1
  • 90 parts by weight of the P(LLA-b-3HP) copolymer prepared in Preparation Example 1-1 and 10 parts by weight of the PDLA polymer prepared in Preparation Example 2-1 were put in a stirring reactor, and stirred at atmospheric pressure (760 Torr) at 200 °C for 30 minutes to prepare a polylactate stereocomplex.
    • Examples 2 to 6 and Comparative Examples 1 to 3
  • Each polylactate stereocomplex was prepared in the same manner as in Example 1, except that substances described in Table 2 below were used as P(LLA-b-3HP) (or PLLA) and PDLA, and the content of PDLA was controlled as described in Table 2 below.
    • Comparative Example 4
  • A commercially available PLLA polymer, Ingeo™ Biopolymer 2003D (PLA 2003 D) produced by Nature Works, was used as Comparative Example 2.
    • [Experimental Example]
  • Physical properties were evaluated for the polymers prepared in Preparation Examples and the polylactate stereocomplexes of Examples and Comparative Examples by the following methods, and the results are shown in Tables 1 and 2.
    • Experimental Example 1: Gel Permeation Chromatography (GPC) Analysis
  • A weight average molecular weight (Mw) and a number average molecular weight (Mn) of each polymer were determined by gel permeation chromatography (GPC) (Waters: Waters707). A polydispersity index (PDI) was calculated by dividing the measured weight average molecular weight by the number average molecular weight.
  • The polymer to be measured was dissolved in chloroform to a concentration of 4000 ppm, and 100 µl thereof was injected into GPC. Chloroform was used as a mobile phase of GPC, a flow rate was 1.0 mL/min, and analysis was performed at 35°C. As a column, four Waters HR-05,1,2,4E were connected in series. RI and PAD detectors were used as detectors, and the measurement was performed at 35°C.
    • Experimental Example 2: Differential Scanning Calorimetry
  • A melting enthalpy and a melting temperature were measured using a differential scanning calorimeter (DSC, manufacturer: Mettler Toledo) by the following method.
  • The polymer (or stereocomplex) was heated to 230 °C, and then maintained for 5 minutes, and the temperature was decreased to -40 °C to remove thermal history, and then heated to 230 °C and the melting temperature (Tm) and the melting enthalpy (ΔH) were measured from a peak of the secondary heating. At this time, the heating and cooling rates were controlled to 10 °C/min, respectively.
    • Experimental Example 3: Measurement of Elongation
  • Elongation was measured for the stereocomplexes of Examples 1 to 6 and Comparative Example 1, and the P(LLA-b-3HP) copolymer of Preparation Example 1-3 by the following method.
  • Each dogbone-shaped test specimen corresponding to ASTM D638 Type V was prepared at 170 °C using a hot-press (Limotem QM900S) device.
  • The elongation was measured for the prepared specimen according to a measurement method of IPC-TM-650 using a tensile strength meter (manufacturer: Instron, model name: 3345 UTM). [Table 1]
    Molecular weight of P3HP Content of P3HP*1 Mn Mw PDI Tm (°C) ΔH (J/g)
    Preparation Example 1-1 10,000 10 89,600 124,000 1.4 171 22.0
    Preparation Example 1-2 10,000 20 57,300 80,000 1.4 169 31.4
    Preparation Example 1-3 25,000 20 88,200 115,100 1.3 162 33.5
    Preparation Example 1-4 25,000 40 41,000 70,000 1.7 159 29.3
    Preparation Example 1-5 25,000 70 21,000 30,000 1.4 153 19.5
    Preparation Example 1-6 PLLA 55,140 118,000 2.1 172 34.8
    Preparation Example 2-1 PDLA 8,700 14,690 1.6 156 46.8
    Preparation Example 2-2 PDLA 29,800 50,000 1.7 162 27.9
    Preparation Example 2-3 PDLA 88,300 120,000 1.4 169 34.3
    *1 parts by weight with respect to 100 parts by weight of poly(L-lactate) repeating unit
    [Table 2]
    P(LLA-b-3HP) or PLLA PDLA (wt%)*2 Elongation(%) Tm (°C) ΔH (J/g)
    Example 1 Preparation Example 1-1 Preparation Example 2-1 (10) 30 201 31.7
    Example 2 Preparation Example 1-2 Preparation Example 2-1 (10) 47 220 33.8
    Example 3 Preparation Example 1-3 Preparation Example 2-1 (10) 92 205 21.5
    Example 4 Preparation Example 1-3 Preparation Example 2-2 (10) 55 213 46.0
    Example 5 Preparation Example 1-4 Preparation Example 2-1 (10) 110 207 11.1
    Example 6 Preparation Example 1-4 Preparation Example 2-1 (20) 100 204 11.0
    Comparative Example 1 Preparation Example 1-6 Preparation Example 2-1 (10) 1.25 211 20.5
    Comparative Example 2 Preparation Example 1-5 Preparation Example 2-1 (10) - 157 17.5
    Comparative Example 3 Preparation Example 1-3 Preparation Example 2-3 (10) 5 207 64.0
    Comparative Example 4 PLA 2003D 1.25 152 39.3
    Preparation Example 1-3 Preparation Example 1-3 - 100 162 33.5
    *2 Content of PDLA in polylactate stereocomplex
  • Referring to Table 2, it was confirmed that the stereocomplexes of Examples 1 to 6 exhibited remarkably improved heat resistance property, as compared with the P(LLA-b-3HP) copolymer alone or the commercially available polylactate resin, and had remarkably improved tensile elongation, as compared with the stereocomplex of Comparative Example 1 prepared from poly(L-lactate) and poly(D-lactate).
  • Meanwhile, Comparative Example 2, in which P(LLA-b-3HP) including more than 50 parts by weight of the poly(3-hydroxypropionate) repeating unit was used, exhibited the melting temperature of lower than 200 °C, indicating that the complex was not formed. Further, Comparative Example 3, in which PDLA having a weight average molecular weight of more than 100,000 g/mol was used, showed formation of the stereocomplex, but its tensile elongation characteristic was remarkably reduced, as compared with those of Examples 1 to 6.
  • These results suggest that when P(LLA-b-3HP) meeting the content of the poly(3-hydroxypropionate) repeating unit within the range of 10 parts by weight or more to 50 parts by weight or less and PDLA having a weight average molecular weight of 5,000 g/mol or more to less than 100,000 g/mol were used, it is possible to prepare a stereocomplex having excellent heat resistance and tensile elongation.

Claims (11)

  1. A polylactate stereocomplex, comprising:
    a poly(L-lactate-3-hydroxypropionate) block copolymer including 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit; and
    a poly(D-lactate) having a weight average molecular weight of 5,000 g/mol or more to less than 100,000 g/mol, wherein the weight average molecular weight is measured by gel permeation chromatography as disclosed in the specification.
  2. The polylactate stereocomplex of claim 1, comprising 70 parts by weight to 90 parts by weigh of the poly(L-lactate-3-hydroxypropionate) block copolymer, and 10 parts by weight to 30 parts by weight of the poly(D-lactate).
  3. The polylactate stereocomplex of claim 1, wherein the poly(L-lactate-3-hydroxypropionate) block copolymer has a weight average molecular weight of 10,000 g/mol to 400,000 g/mol, wherein the weight average molecular weight is measured by gel permeation chromatography as disclosed in the specification.
  4. The polylactate stereocomplex of claim 1, wherein the poly(D-lactate) has a weight average molecular weight of 15,000 g/mol to 50,000 g/mol.
  5. The polylactate stereocomplex of claim 1, wherein a melting temperature of the polylactate stereocomplex is 200 °C or higher, wherein the melting temperature is measured by differential scanning calorimetry as disclosed in the specification.
  6. The polylactate stereocomplex of claim 1, wherein a melting enthalpy of the polylactate stereocomplex is 11 J/g or more, wherein the melting enthalpy is measured by differential scanning calorimetry as disclosed in the specification.
  7. The polylactate stereocomplex of claim 1, wherein the polylactate stereocomplex has elongation of 10 % or more, as measured in accordance with IPC-TM-650 using a tensile strength tester after preparing a dogbone-shaped test specimen of ASTM D638 Type V.
  8. A method of preparing a polylactate stereocomplex, the method comprising the step of mixing a poly(L-lactate-3-hydroxypropionate) block copolymer including 10 parts by weight to 50 parts by weight of a poly(3-hydroxypropionate) repeating unit with respect to 100 parts by weight of a poly(L-lactate) repeating unit and a poly(D-lactate) having a weight average molecular weight of 5,000 g/mol or more to less than 100,000 g/mol.
  9. The method of claim 8, wherein the poly(L-lactate-3-hydroxypropionate) block copolymer is prepared by a ring-opening polymerization of a lactide monomer in the presence of a poly(3-hydroxypropionate) initiator.
  10. The method of claim 9, wherein the poly(3-hydroxypropionate) initiator has a weight average molecular weight of 1,500 g/mol to 50,000 g/mol.
  11. The method of claim 9, wherein the content of the poly(3-hydroxypropionate) initiator is 10 parts by weight or more with respect to 100 parts by weight of the lactide monomer.
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